CN1278747A - Catalyst for membrane electrode assembly and method of making - Google Patents
Catalyst for membrane electrode assembly and method of making Download PDFInfo
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- CN1278747A CN1278747A CN98811189A CN98811189A CN1278747A CN 1278747 A CN1278747 A CN 1278747A CN 98811189 A CN98811189 A CN 98811189A CN 98811189 A CN98811189 A CN 98811189A CN 1278747 A CN1278747 A CN 1278747A
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Abstract
Nanostructured elements are provided for use in the electrode of a membrane electrode assembly for use in fuel cells, sensors, electrochemical cells, and the like. The nanostructured elements comprise acicular microstructured support whiskers bearing acicular nanoscopic catalyst particles which may comprise alternating layers of catalyst materials, which may comprise a surface layer that differs in composition from the bulk composition of the catalyst particles, and which may demonstrate improved carbon monoxide tolerance.
Description
Technical Field
The present invention relates to nanostructured catalysts for use in fuel cells and sensors, and in particular to catalysts that exhibit good resistance to carbon monoxide poisoning. The invention also relates to a method for preparing the catalyst and a fuel cell and a sensor using the catalyst.
Background
Electrochemical cells, including proton exchange membrane fuel cells, sensors, electrolyzers, and electrochemical reactors, are known in the art. Typically, the central component of such electrochemical cells is a membrane electrode assembly, comprising two catalytically acting electrodes separated by an Ion Conducting Membrane (ICM), commonly referred to as a Membrane Electrode Assembly (MEA). In a fuel cell, the MEA is sandwiched between two porous, electrically conductive backing layers to form a 5-layer assembly. When a 3-layer MEA comprises a polymer membrane in the middle, the fuel cell is commonly referred to as a Polymer Electrolyte Fuel Cell (PEFC). In a typical low temperature fuel cell, hydrogen is oxidized at the anode and oxygen (usually air) is reduced at the cathode:
pt (anode) Pt (cathode)
2e-(via circuit) →
Fuel cell MEAs have been fabricated with catalyst electrodes in the form of Pt particles or an applied dispersion of a carbon-supported Pt catalyst. These conventional catalysts are applied to the ICM or to the backing layer adjacent to the membrane in an electrolyte-containing ink or paste. The main catalyst form for hydrogen-fuel polymer electrolyte membranes is Pt or a Pt alloy coated on large carbon particles by wet chemical methods such as chloroplatinic acid reduction. The catalyst, in conventional form, is dispersed in an ionomer binder, solvent, and often Polytetrafluoroethylene (PTFE) particles to form an ink, paste or dispersion, which is then applied to a membrane or electrode backing material. In addition to serving as a mechanical support, the carbon support particles are generally recognized in the art as providing the desired electrical conductivity within the electrode layer.
In another variation, the catalyst metal salt is reduced in an organic solution of a solid polymer electrolyte to form a dispersion of catalyst metal particles in the electrolyte (without support particles) which is then cast onto an electrode backing layer to form the catalyst electrode.
In yet another variation, the Pt particles are mixed directly into a solution of solvent and polymer electrolyte and then coated onto the electrode backing layer. However, this method results in very high catalyst loading and therefore very high cost due to the inability to produce very fine particles and the dispersion stability limitations.
Conventional catalyst alloy particles are typically made by wet chemical or metallurgical processes and supported on conventional carbon support particles. Conventional particles have a uniform composition, roughly spherical morphology (indicating that conventional processes produce particles with a habit of crystallite growth) representing the alloy stoichiometry, and are randomly dispersed over the surface of large support particles. The catalyst particles may also be used without a support as a "black mass". The diameter of these particles is reported to be in the range of 2 to 25 nanometers, increasing with increasing amounts of catalyst on each support particle.
Various other structures and means have been employed to apply or otherwise bring the catalyst into contact with the electrolyte to form the electrodes. These MEAs may include: (a) a planar distribution of porous metal films or metal particles or carbon supported catalyst powders deposited on the surface of the ICM; (b) a metal grid or mesh deposited on or embedded in the ICM; or (c) a catalytically active nanostructured composite element embedded in the surface of the ICM.
PEFC has been found to be a potential energy source, for example for electric vehicles, as PEFC has been shown to have good energy conversion efficiency, high power density and negligible pollution. In a vehicle such as an automobile, a convenient source of hydrogen gas may be steam reforming of methanol, since methanol is more readily stored in the vehicle than hydrogen. However, it is known that methanol reformate gas can contain up to 25% dioxide (CO)2) And 1% carbon monoxide (CO), whereas the catalytic performance of pure platinum can be significantly reduced in the presence of even 10 parts per million (ppm) CO. Thus, successful use of reformed hydrogen fuel depends on reducing the CO content in the fuel or developing a CO tolerant catalyst, or both.
Two approaches have been reported in the art to avoid the impact of CO on PEFC performance. The first method is the oxidation of CO at the anode to CO by introducing air (typically at 2% by volume) into a reforming hydrogen stream2(as described in U.S. patent 4,910,099). While this approach is effective, it adds added complexity to the PEFC and reduces its efficiency. A second approach is to alloy a Pt electrode with a second element, preferably ruthenium (Ru), to increase The resistance of The Pt electrode to CO (see, e.g., M.Iwase and S.Kawatsu, electrochemical society Proceedings, V.95-23, p.12; Proceedings of The First International Symposium on Proceedings Membrane Fuel Cell, edited by S.Gottesfeld et al, The electrochemical society, Pennington, NJ, 1995). Tolerance to up to 100ppm CO was obtained when the fuel cell was operated at 80 ℃ with a Pt/Ru atomic ratio of 1: 1 for a Pt loading of 0.4 mg/cm alloy on a carbon support. It is also known in the art (T.A. Zawdazinski, Jr., Fuel Cells for transfer, US Department of energy, NAtional Laboratory R&D Meeting, 22-23 days 7 months 1997, Washington, DC), PtRu loading of 0.6 mg/cm, PEFC operating at temperatures above 100 ℃ was shown to be able to tolerate 100 ℃ppm CO. However, this process fails at low temperature operation or when lower loading of catalyst is employed.
Some nanostructured composite articles have been disclosed. See, for example, U.S. patents 4, 812, 352, 5, 039, 561, 5, 176, 786, 5, 336, 558, 5, 338, 430 and 5, 238, 729. U.S. patent No. 5,338,430 discloses nanostructured electrodes embedded in solid polymer electrolytes that perform better than conventional electrodes using metal particles or carbon-supported metal catalysts, with advantages including: expensive catalyst materials can be used more efficiently and the catalytic activity is greater.
Summary of The Invention
Briefly, the present invention provides nanostructured elements for use in electrochemical cells, which elements comprise acicular microcarrier whiskers bearing acicular nanoscopic (nanoscopic) catalyst particles, and methods and apparatus for making the elements. The catalysts of the present invention demonstrate improved performance of PEFC anode catalysts for hydrogen oxidation in the presence of carbon monoxide. The catalyst of the present invention can be used for MEA in fuel cells, sensors, electrolyzers, chlor-alkali separation membranes, etc.
In another aspect, the present invention provides a method of making the nanostructured elements of the invention. The catalyst article of the present invention is prepared by: the catalyst is vacuum coated onto the microstructure in multiple layers such that the catalyst forms acicular nanoscopic catalyst particles supported on the microstructure. This structure provides an extremely high surface area to volume ratio for the catalyst material. At the same time, the process allows control over catalyst composition and morphology, which has not previously been possible. For example, alternating layers of different catalyst materials may be deposited. The degree of crystallinity and the degree of alloying can be controlled. In addition, the surface composition of the final catalyst can be adjusted independently of the overall composition of the catalyst.
In another aspect, the present invention provides a catalyst that demonstrates improved carbon monoxide tolerance in fuel cell applications.
In yet another aspect, the present invention provides an electrochemical device comprising a fuel cell having a nanostructured element of the present invention inserted therein.
In the present application:
"membrane electrode assembly" refers to a structure comprising a membrane comprising an electrolyte and at least one, but preferably two or more, electrodes adjacent to the membrane;
"growth surface" refers to that portion of the surface on which the deposition material is preferentially incorporated for the nanoscale catalyst particles;
"nanostructured elements" refer to finely divided micro-scale (microscopic) structures comprising nano-scale catalyst material on at least a portion of their surface;
"microstructure" refers to a micron-scale structure that is dispersed like a pointer;
"nanosized catalyst particles" means particles of catalyst material having at least one dimension equal to or less than about 10 nanometers, or a crystallite size of about 10 nanometers or less (as measured by the half width of the diffraction peak of a standard 2-theta x-ray diffraction scan);
"acicular" means a ratio of length to average cross-sectional width of greater than or equal to 3;
"disperse" is the presence of other fine portions that are physically discontinuous with respect to each other, but does not preclude the portions from contacting each other; and
"micron-sized" means having at least one dimension equal to or less than about 1 micron.
It is an advantage of the present invention to provide a catalyst in the form of nanostructured elements having a very high surface area to volume ratio, controllable composition and morphology, and superior CO tolerance.
Brief Description of Drawings
Figure 1 is a field emission scanning electron micrograph of a nanostructured element according to the invention on its initial substrate taken at 40000 times magnification.
Figure 2 is a transmission electron micrograph taken at 270000 magnification of individual acicular support particles of the present invention coated with acicular nanoscopic catalyst particles.
Fig. 2A is a detail of fig. 2.
Figure 3 is a transmission electron micrograph taken at 270000 magnification of individual acicular support particles of the present invention coated with acicular nanoscopic catalyst particles.
FIG. 4A is a schematic diagram of an apparatus for carrying out the method of the present invention.
FIG. 4B is a schematic diagram of an apparatus for carrying out the method of the present invention.
Fig. 5 shows the current density versus cell voltage for 10 fuel cells of the present invention.
Fig. 6 shows the current density versus time for a fuel cell of the invention and a comparative fuel cell.
Detailed description of the preferred embodiments
The catalyst particles of the present invention comprise elongated or acicular nanoscale particles having a size equal to or less than about 10 nanometers. Catalyst particles are prepared by vacuum deposition of catalyst material onto a support having an acicular microstructure of about 1 micron or less in size. In the deposition process of the present invention, the catalyst particles increase in length rather than diameter primarily as the amount of catalyst on each support particle increases. The catalyst particles of the present invention may be alternating layers of different catalyst materials that differ in composition, degree of alloying, or crystallinity. By varying the thickness of each monolayer, the overall stoichiometry and degree of alloying can be varied. The surface composition of the catalyst particles can be controlled by controlling the on or off of the deposition source and how much power is supplied to the deposition source during thelast few passes in front of the deposition source. The surface composition of the catalyst particles may be different from the composition of the bulk of the particles.
The inventive nanosized catalyst particles are shown in fig. 1, wherein field emission scanning electron micrographs of the inventive nanostructured elements still on the original substrate prior to transfer to the ICM are shown, and transmission electron micrographs of individual acicular support particles coated with acicular nanosized catalyst particles are shown in fig. 2 and 3, respectively.
Fig. 2 is a transmission electron micrograph of a portion of a catalyst coated support particle of the present invention. The acicular support particles are perylene red (PR149) whiskers with alternating layers of Pt and Ru at a catalyst loading of 0.42 mg/cm. Fig. 2 shows that the two-way catalyst coating contains smaller, densely packed but dispersed acicular particles that are uniformly oriented slightly off-normal to the sides of the PR149 support particle core. The nanosized acicular catalyst particles have a diameter of only about 8-9 nanometers and a length of about 50 nanometers in this example. For example, the acicular nanoscopic particles shown in the inset (fig. 2A) are 55 nanometers long and 9.3 nanometers in diameter. For lower or higher catalyst loadings on the electrode, the length of the catalyst particles is shorter or longer than in this example because the acicular particles grow longer with increasing loading.
It is observed from the crystalline and amorphous catalyst particles that the catalyst particles have the same type of columnar or acicular growth morphology on the side of the support particle. FIG. 3 shows amorphous PtO coated onto PR149 support particlesxSuch nodular growth of (a). In this example, the aspect ratio of the catalyst particles is considerably low because the catalyst loading isconsiderably low. Such catalyst particles grow as the loading amount increases.
Figure 2 also demonstrates that the individual acicular catalyst particles are crystalline, layered. The electron micrographs show interference bands in the TEM images due to stacking faults in some of the grains. These appear as light and dark bands perpendicular to the length of the catalyst particles. This is direct evidence that individual acicular catalyst particles contain crystalline material. X-ray diffraction theta-2 theta scans of these catalysts show that Pt Ru is a hybrid alloy with a Pt-type face-centered cubic lattice (FCC). For the FCC lattice, only dense (111) lattice planes can show stacking faults, indicating that the catalyst particles showing banding contain grains with a [111]growth axis. (FIG. 2 shows that only some of the catalyst particles have interference bands due to the conditions required for electron interference to occur, including the proper location and orientation of the particles.
While not wishing to be bound by theory, some conclusions may be drawn as to the composition of the needle catalyst particle alloy. The conditions used to prepare the samples shown in fig. 2 were the same as those described for samples 3-5 of example 6, except that the sputtering time was 50 minutes, giving a total of 0.43 mg/cm. Example 6 shows that these binary catalysts are rich in Ru (Pt: Ru = 35: 65 wt%), and X-ray diffraction theta-2 theta scans of this series of samples show that two crystalline phases are obtained, one with a Pt face-centered cubic lattice structure and PtRu2Stoichiometric crystalline alloy, the second being the Ru crystalline phase. The stacking faults shown in the acicular crystal particles of FIG. 2 may be combined with alternating PtRu2The interface between the crystalline and Ru phases is relevant. In other words, during the deposition growth of the crystalline particles, the Ru-rich crystalline phase separates into PtRu2Alternating layers of alloy and pure Ru. At the drum speed and deposition rate used for the sample of fig. 2, the drum was rotated 73 times during the 50 minute coating period, resulting in a mass deposition of PtRu equivalent to about 290 nm being applied to the surface. This implies that about 4 nm/revolution of material is added to the surface. Assuming the material is applied centrally at the end of the needle-like crystals, the layer thickness is of the same order of magnitude as the d (111) lattice spacing obtained by fitting the X-ray diffraction peaks discussed in example 6.
The vehicle of the microstructure suitable for use in the present invention may comprise whiskers of an organic pigment, the most preferred organic pigment being c.i. pigment RED 149 (perylene RED). The whiskers have a substantially uniform but non-uniform cross-section and have a high aspect ratio. The microstructured support whiskers are deposited with a material suitable for use as a catalyst, such that the whiskers have a fine nanoscale surface structure that can function as a plurality of catalytic sites.
Methods of preparing microstructured layers are known in the art. For example, methods for preparing organic microstructured layers are disclosed in the following documents: materials Science and Engineering, A158(1992), pages 1-6; J.Vac.Sci.Technol.A, 5, (4)1987, month 7/8, pages 1914-16; J.Vac.Sci.Technol.A, 6, (3), 5/6 months in 1988, pages 1907-11; thin Solid Films, 186, 1990, pages 327-47; mat. sci.25, 1990, pages 5257-68; rapidly queried Metals, Proc. of the Fifth int. Conf. on Rapidly queried Metals, Wurzburg, Germany (9.3-7.1984), S.Steeb et al, eds., Elsevier Science Publishers B.V., New York, (1985), pp.1117-24; photo.sci.and eng, 24(4), 7/8 months, 1980, pages 211-16; and U.S. patents 4, 568, 598 and 4, 340, 276. Methods for producing inorganic-based microstructured whisker layers are disclosed, for example, in the following documents: J.Vac.Sci.Tech.A, 1, (3), 7/9 months in 1983, 1398-; U.S. Pat. nos. 3,969,545; and U.S. patents 4, 252, 865, 4, 396, 643, 4, 148, 294, 4, 252, 843, 4, 155, 781, 4, 209, 008 and 5, 138, 220; k.robbie, l.j.friedrich, s.k.dew, j.smy and m.j.brett, j.brett, j.vac.sci.technol.a 13(3), 1032(1995) and k.robbie, m.j.brett and a.lakhtokia, j.vac.sci.technol.a 13(6), 2991 (1995).
The orientation of the microstructure is generally uniform relative to the substrate surface. The microstructures are generally oriented perpendicular to the original substrate surface, with the perpendicular (normal) direction of the surface defined as the direction of a line perpendicular to an imaginary plane that is tangent to the substrate surface at the point of contact between the bottom of the microstructure and the substrate surface. It can be seen that the surface normal varies with the contour of the substrate surface. The major axes throughout the microstructure may or may not be parallel to each other.
In addition, the shape, size, and orientation of the microstructures may also be non-uniform. For example, the top of the microstructure may be curved, curled or curved, or the microstructure may be curved, curled or curved over its entire length.
Preferably, the microstructures are of uniform length and shape throughout and have uniform cross-sectional dimensions along their major axes. The length of each microstructure is preferably less than about 50 microns. More preferably, the length of each microstructure is in the range of about 0.1 to 5 microns, most preferably in the range of 0.1 to 3 microns. In any of the microstructure layers, the microstructures preferably have a uniform length. Preferably, each microstructure has an average cross-sectional dimension of less than about 1 micron, more preferably between 0.01 and 0.5 micron. Most preferably, the average cross-sectional dimension of each microstructure is between 0.03 and 0.3 microns.
The area number density of the microstructures is preferably about 107To 1011Between microstructures per square centimeter, more preferably, at about 108To 1010In the range of one microstructure per square centimeter.
The microstructures can have various orientations, straight and curved shapes (e.g., whiskers, rods, cones, pyramids, spheres, cylinders, laths, etc., which can be twisted, bent, or straight), and any layer can have various combinations of orientations and shapes.
The microstructure preferably has a height to diameter ratio (i.e., length to diameter ratio) in the range of about 3: 1 to about 100: 1.
Materials useful as substrates include those that remain intact under the conditions used to form the microstructures. The substrate may be flexible or rigid, planar or non-planar, convex, concave, textured, or a combination thereof.
Preferred substrates include organic and inorganic materials (including, for example, glass, ceramics, metals, and semiconductors). Preferred inorganic substrates are glass and metal. The preferred organic substrate is polyimide. More preferably, the substrate is metallized with a conductive metal layer of 10 to 70 nanometers thick to remove electrostatic charge. This layer may be discontinuous. Preferably, this layer is the same metal used to coat the microstructured whiskers.
Typical organic substrates include those that are stable at annealing temperatures, for example, polymers such as polyimide films (e.g., available from DuPont Electronics, Wilmington, DE under the trade name "KAPTON"), high temperature stable polyimides, polyesters, polyamides, and polyaramides.
Metals used as substrates include, for example, aluminum, cobalt, copper, molybdenum, nickel, platinum, tantalum, or combinations thereof. Ceramics used as the substrate include, for example, metallic or nonmetallic oxides such as alumina and silica. A useful inorganic nonmetal is silicon.
The layer of organic material capable of forming microstructures is applied to the substrate using techniques known in the art, including, for example, vapor deposition (e.g., vacuum evaporation, sublimation, and chemical vapor deposition), and solution or dispersion coating (e.g., dip coating, spray coating, spin coating, knife coating, bar coating, roll coating, and pour coating (i.e., pouring a liquid onto a surface such that the liquid flows over the surface)). The organic layer is preferably applied by physical vacuum vapor deposition (i.e., sublimation of the organic material under applied vacuum conditions).
Suitable organic materials for creating microstructures (e.g., post-coating plasma etching) include, for example, polymers and prepolymers thereof (e.g., thermoplastic polymers such as alkyd, melamine, urea-formaldehyde, diallyl phthalate, epoxy-based polymers, phenolic polymers, polyesters, and silicones; thermosetting polymers such as acrylonitrile-butadiene-styrene, acetals, acrylics, cellulose, chlorinated polyethers, ethylene-vinyl acetate, fluorocarbons, ionomers, nylon, parylene, phenoxy polymers, heteroisomorphous polymers, polyethylene, polypropylene, polyamide-imide, polyimide, polycarbonate, polyesters, polyphenylene oxide, polystyrene, polysulfone, and vinyl polymers); organometallic compounds (e.g., bis (η) (η, a method of plasma etching) and the like5Cyclopentadienyl) iron (II), iron pentacarbonyl, ruthenium pentacarbonyl, osmium pentacarbonyl, chromium hexacarbonyl, molybdenum hexacarbonyl, tungsten hexacarbonyl and tris (triphenylphosphine) rhodium chloride).
Preferably, the organic-based microstructure layer preferably has the same chemical composition as the starting organic material. Preferred organic materials for preparing the microstructured layer include, for example, planar molecules containing substantially delocalized chains or rings of pi-electron density. These organic materials are typically crystallized into a herringbone structure. Preferred organic materials can generally be classified into polynuclear aromatic and heterocyclic aromatic compounds.
Polynuclear aromatics are described in Morrison and Boyd, Organic Chemistry, 3 rd edition, Allyn and Bacon Inc. (Boston: 1974) chapter 30. The heterocyclic aromatic hydrocarbon compounds are described in chapter 31 of the same book.
Commercially preferred polynuclear aromatic hydrocarbons include, for example, naphthalene, phenanthrene, perylene, anthracene, coronene, and pyrene. One preferred polynuclear aromatic hydrocarbon is N, N' -di (3, 5-xylyl) perylene-3, 4, 9, 10 bis (dicarboximide) (available from american hoechst corp. of Somerset, NJ under the trade designation "c.i. piment RED 149"), herein referred to as "perylene RED".
Preferred heterocyclic aromatic compounds that are commercially available include, for example, phthalocyanines, porphyrins, carbazoles, purines, and pterins. Typical examples of the heterocyclic aromatic hydrocarbon compound include, for example, metal-free phthalocyanines (e.g., dihydrophthalocyanines) and metal complexes thereof (e.g., copper phthalocyanines).
Preferably, the organic material is capable of forming a continuous layer when deposited onto the substrate. The thickness of the continuous layer is preferably between 1 nm and 1000 nm.
The orientation of the microstructure is affected by the substrate temperature, deposition rate and angle of incidence at which the organic layer is deposited. If the substrate temperature at which the organic material is deposited is sufficiently high (i.e., exceeds a critical substrate temperature, which in the art is related to 1/3 which is the boiling point (in degrees Kelvin) of the organic material), the deposited organic material will form a randomly oriented microstructure upon deposition or upon subsequent annealing. If the substrate temperature is relatively low (i.e., below the critical substrate temperature) during deposition, the deposited organic material will form a uniformly oriented microstructure upon annealing. For example, if uniform orientation of the perylene red microstructure is desired, the substrate temperature during deposition of the perylene red is preferably between about 0 ℃ and about 30 ℃. Some subsequent coating processes, such as DC magnetron sputtering and cathodic arc vacuum methods, can produce curvilinear microstructures.
If a pattern of microstructures is desired, certain microstructures on the substrate can be selectively removed by, for example, mechanical means, vacuum processing means, chemical means, gas pressure or fluid means, radiation means, and combinations thereof. Useful mechanical methods include, for example, scraping the microstructures from the substrate with a sharp instrument (e.g., a razor), and encapsulating with a polymer, followed by delamination. Useful irradiation methods include laser or photoablation. This ablation may produce a patterned electrode. Useful chemical methods include, for example, etching selected areas of the microstructure layer with an acid. Useful vacuum methods include, for example, ion sputtering and reactive ion etching. Useful air pressure methods include, for example, blowing microstructures from a substrate with a gas (e.g., air) or liquid stream. A combination of the above approaches, such as photoresist and photolithography, may also be used.
The microstructures can be extensions of the substrate and the same as the substrate material, for example, by mask vapor deposition of discrete metal micro-islands (micro-islands) onto the polymer surface, followed by plasma etching or reactive ion etching to remove polymer material not masked by the metal micro-islands, leaving some protrusions of the polymer substrate on the surface thereof, so long as the protrusions are transferred to the ICM.
U.S. Pat. Nos. 4,812, 352 and 5,039,561 disclose a preferred method for preparing organic-based microstructural layers. As disclosed in these articles, a method of preparing a microstructured layer comprises the steps of:
i) vapor depositing or condensing an organic material onto a substrate to form a continuous or discontinuous thin layer; and
ii) annealing the deposited organic layer in a vacuum at a temperature and for a time sufficient to cause a physical change in the deposited organic layer to form a microstructure layer comprising a densely packed discontinuous microstructure, but at a temperature insufficient to cause evaporation or sublimation of the organic layer.
For different film thicknesses, there may be the most suitable maximum annealing temperature in order to fully transform the deposited layer into a microstructure. After complete transformation into microstructures, the major dimension of each microstructure is proportional to the thickness of the organic layer initially deposited. Since the microstructures are discontinuous, are spaced apart by a distance of about the size of their cross-section, preferably uniform, and all of the original organic film is transformed into microstructures, conservation of weight means that the length of the microstructures will be proportional to the thickness of the layer initially deposited. Due to this relationship of the original organic layer thickness to the length of the microstructure, and the cross-sectional dimension is independent of length, the length and aspect ratio of the microstructure can be varied independently of its cross-sectional dimension and area density. For example, it has been found that the microstructure length is about 10-15 times the thickness of the vapor deposited perylene red layer when the thickness is between about 0.05 and 0.2 microns. The surface area of the microstructured layer (i.e., the sum of the individual microstructured surface areas) is much greater than the surface area of the organic layer initially deposited on the substrate. The thickness of the initially deposited layer is preferably in the range of about 0.03 to 0.5 microns.
Each individual microstructure may be single crystal or polycrystalline, rather than amorphous. The microstructure layer may have a high degree of anisotropy due to its crystalline nature and uniform orientation.
If a discontinuous distribution of microstructures is desired, a mask may be used to selectively coat specific areas of the substrate during the organic layer deposition step. Other techniques known in the art for selectively depositing organic layers onto specific areas of a substrate may also be employed.
In the annealing step, the substrate coated with the organic layer is heated under vacuum for a time and at a temperature sufficient to cause a physical change in the coated organic layer, wherein the organic layer grows into a microstructure layer in which a plurality of individual microstructures, which are densely packed and discontinuous, oriented single crystals or polycrystals, are present. When the substrate temperature at the time of deposition is very low, uniform orientation of the microstructure is an inherent result of the annealing process. No adverse effect on subsequent microstructure formation was observed from exposure of the coated substrate to atmospheric air prior to the annealing step.
For example, if the organic material being coated is perylene red or copper phthalocyanine, the annealing is preferably under vacuum (i.e., less than about 1 x 10-3Torr), 160 to 270 deg.c. The annealing time required to transform the initial organic layer into a microstructure layer depends on the annealing temperature. Generally, an annealing time in the range of about 10 minutes to about 6 hours is sufficient. Preferably, the annealing time is in the range of about 20 minutes to 4 hours. Furthermore, in the case of perylene red, the optimum annealing temperature to convert all the initial organic layers into a microstructured layer without sublimating it was observed to vary with the thickness of the deposited layer. Typically, for an initial organic layer having a thickness of 0.05 to 0.15 microns, the temperature is in the range of 245-270 ℃.
The time interval between the vapor deposition step and the annealing step can vary from a few minutes to several months without significant adverse effects, as long as the coated composite is stored in a closed container to minimize contamination (e.g., dust). As the microstructure grows, the intensity of the infrared band of the organic material changes and the laser specular reflectivity decreases, so that this transition can be carefully monitored in situ by, for example, surface ir spectroscopy. After the microstructure has grown to the desired size, the layer structure comprising the substrate and the microstructure is allowed to cool and then placed under atmospheric pressure.
Useful inorganic materials for creating microstructures include, for example, carbon, diamond-like carbon, ceramics (e.g., oxides of metals or non-metals, such as aluminum oxide, silicon oxide, iron oxide, and copper oxide; nitrides of metals or non-metals, such as silicon nitride and titanium nitride; and carbides of metals or non-metals, such as silicon carbide; borides of metals or non-metals, such as titanium boride); metallic or nonmetallic sulfides such as cadmium sulfide and zinc sulfide; metal silicides such as magnesium silicide, calcium silicide, and iron silicide; metals (e.g., noble metals such as gold, silver, platinum, osmium, iridium, palladium, ruthenium, and rhodium and combinations thereof; transition metals such as scandium, vanadium, chromium, manganese, cobalt, nickel, copper, zirconium, and combinations thereof; low melting point metals such as bismuth, lead, indium, antimony, tin, zinc, and aluminum; refractory metals such as tungsten, rhenium, tantalum, molybdenum, and combinations thereof); and semiconductor materials (e.g., diamond, germanium, selenium, arsenic, silicon, tellurium, gallium arsenide, gallium antimonide, gallium phosphide, aluminum antimonide, indium tin oxide, zinc antimonide, indium phosphide, aluminum gallium arsenide, zinc telluride, and combinations thereof).
As described above, the microstructures of the preferred embodiments can be made to have random orientation by controlling the substrate temperature during the deposition of the initial PR149 layer. The microstructure can also be made to have a curved shape by taking appropriate conditions for the coating process. As described in figure 6 of l.aleksandov, chapter 1, Elsevier, New York, 1984, "growth of crystals of semiconductor material on crystal surfaces", the energy to atoms in different coating methods (e.g., thermal evaporation deposition, ion deposition, sputtering, and implantation) can be in the range of 5 orders of magnitude.
It is also within the scope of the present invention to modify the method of making the microstructure layer to produce a discontinuous microstructure distribution.
The coating material comprising the nano-sized catalyst particles is preferably a catalyst material or a material that imparts catalytic properties to the overall nanostructured elements. The coating material may be an inorganic material or an organic material, including a polymeric material. Useful inorganic coating materials can include those described in the microstructure section above. Useful organic materials include, for example, conductive polymers (e.g., polyacetylene), polymers derived from polyparaxylylene, and materials capable of forming self-assembled layers.
The coating may be formed by deposition onto the microstructured layer using a vapor deposition process such as ion sputter deposition, cathodic arc deposition, vapor condensation, vacuum sublimation, physical vapor transport, chemical vapor transport, and metal organic chemical vapor deposition, as described below. Preferably, the conformably coated material is a catalyst metal or metal alloy.
Key aspects of the prepared acicular carriers for nanostructures are: it can be easily transferred from the original substrate to the membrane or EBL surface to form the MEA catalyst electrode layer; it allows more catalyst particles to be deposited on its surface, preferably at least 80% by weight (based on the combined weight of the support and catalyst particles) of the catalyst particles deposited on its surface; it has sufficient number density and height to diameter ratio to provide a large support surface area for the catalyst, which is at least 3-5 times the planar area of the substrate, but more preferably 10-15 times the planar area of the substrate; the shape and orientation of the acicular support particles on the initial substrate helps the catalyst particles to be uniformly coated into the acicular texture morphology.
It has been described in the art that vapor deposition of thin films on planar substrates at nearly parallel angles of incidence results in oriented, discontinuous columnar growth due to shadowing (shadowing) effects. This method is described in j.van de waterbed, g.van Oosterhout, Philips res.repts., 22, 375-.
However, the results obtained with the present invention are unexpected: deposition at near normal incidence on a film planar substrate already having oriented but discontinuous microstructures (as is the case with acicular carrier particles) allows much smaller discontinuous nanoscale structures to grow on the sides of the individual microstructures. Such fractional value (fractional) like structures should be close to having the largest surface area. This effect is of particular practical significance in the field of catalysis, since the electrochemical activity of the catalyst electrode is directly related to the active surface area of the catalyst, which in turn is directly related to the total geometric surface area.
In the present invention, vacuum deposition may be achieved by any suitable means known in the art. An apparatus for vacuum deposition generally comprises a vacuum chamber including a vacuum pump, a source or target, a substrate, and a means for generating a substance to be deposited.
Chemical Vapor Deposition (CVD) processes may be used to vacuum deposit materials resulting from chemical reactions that occur as reactants flow through a heated substrate and react at or near the surface of the substrate to form a thin film. CVD methods may include, for example, plasma-assisted CVD, photo-activated CVD, metal-organic CVD, and related methods.
Preferably, the catalyst and catalyst structures of the present invention can be manufactured by Physical Vapor Deposition (PVD). PVD methods involve depositing atoms or molecules or combinations thereof, typically by evaporation or sputtering under vacuum. The PVD method is characterized by the following steps: (1) generating a deposition substance by evaporation in a manner of resistance, inductance, sputtering by electron beam heating, laser beam ablation, direct current plasma generation, radio frequency plasma generation, molecular beam epitaxy or the like; (2) transporting the deposition material from the feedstock to the substrate by means of molecular flow, viscous flow, plasma gas transport, or the like; and (3) performing film growth on the substrate, which may be assisted by biasing the substrate. PVD can use various substrate temperatures to control the crystallization and growth of the deposited material.
Physical vapor sputtering deposition is carried out under partial vacuum (diode system 13.3 to 1.33 pa, magnetron system 0.13 to 0.013 pa) while the target (usually the cathode) is bombarded with gas ions accelerated by an electric field. The sputtering gas is typically an inert gas such as argon, but may also include reactive elements that can be incorporated into the deposited film, for example in the case of nitride, oxide, and carbide deposition. When the sputtering gas is ionized, a glow discharge or plasma is generated. The gas ions are accelerated towards the target by an electric field or an electric and magnetic field. By momentum transfer, atoms of the target are ejected and move through the vacuum chamber to be deposited on the substrate. The target may typically be a single elemental species.
Alloy deposition can be achieved by co-evaporation of multiple target elements by evaporation or sputtering from a single alloy source, and rapid evaporation of preformed alloy particles. PVD of alloys by methods known in the art is not satisfactory, mainly for the following reasons: the compositions of the alloys typically have different vapor pressures and sputtering rates (sputtering yields), and they may change over time, such that the resulting alloy on the target may differ from the composition of the target alloy. Multi-source co-evaporation or sputtering methods typically result in variations in the alloy composition along the plane of the substrate; rapid evaporation, pulsed laser evaporation and electron beam evaporation can cause droplets to be emitted, resulting in large defects on the substrate.
The deposition of mixed metal or alloy catalysts by vacuum deposition methods can be accomplished using a single mixed catalyst source. However, it is difficult to control the stoichiometric ratio due to the difference in the sputtering rate or the evaporation/sublimation rate of different elements. Another approach is to co-deposit multiple sources of different elements onto the same area of the substrate at the same time. However, due to the physical size of the actual device, the angle of incidence at which the substrate can be reached is limited, and it is difficult to perform uniform deposition on the substrate due to the different distances from the sources. In addition, the deposition sources can contaminate each other.
A preferred method of vacuum deposition of a mixed metal or alloy catalyst according to the present invention is to sequentially deposit several layers of alternating elemental compositions. These difficulties are avoided by using a multi-layer, ultra-thin layer vacuum deposition process to produce an alloy or multi-element catalyst. In addition, it may also be desirable to apply one material using sputtering gas conditions that are different from those used to apply the other material, such as reactive sputtering deposition for one element and non-reactive sputtering deposition for another element.
The deposition rate is controlled by the setting of the power of the deposition source and the throw distance between the target source and the substrate, while the deposition amount per pass is controlled by the deposition rate and the pass time. Thus, with a combination of multiple target source powers and drum speeds, a fixed deposition amount per pass under the target can be obtained. The deposition amount per pass can be different, from 10 on the low end15Sub-monolayers in the atomic/cm or lower range are doped discontinuously to hundreds of atomic layers at the high end. Depending on the film growth mechanism and sputtering conditions characteristic of the deposited material, the material may nucleate islands in a continuous film or discontinuous fashion. In this way, the deposition can be controlled, as in the case of atomic layer epitaxy, to control the catalyst structure and composition in a range from lattice units to multilayer morphologies, and from disordered films to superlattice-like structures (in which both alloy phases and crystalline phases of the individual elements are present). The amount per pass may vary from 1/10 atomic monolayers to hundreds of atomic monolayers, but is preferably between 1 and 100 monolayers, more preferably between 5 and 50 monolayers.
Fig. 4A and 4B show two possible device configurations for multi-layer vacuum deposition in the present invention. In these embodiments, two or more vacuum deposition stations are placed in front of an actuator supporting the substrate, which actuator moves the substrate in different deposition spaces defined by the vacuum deposition stations. In fig. 9B, the substrate in the form of a semi-continuous strip is passed completely in a straight line in front of a series of vapor sources (e.g., sputtering or evaporation sources), one sequential deposition of layers is performed, then the direction is reversed for another deposition, and the cycle is repeated as many times as necessary. Either of these two methods has a higher ability to modify the surface composition than the other two methods of vacuum coating a mixed metal catalyst layer described above.
In a preferred embodiment, the catalyst coating is applied to the support particles by a sputter deposition process using a system of the type shown in fig. 4A and 4B. For coating a continuous substrate, the straight line process shown in fig. 4B is preferred. The apparatus consisted of three source magnetron sputtering systems arranged around the outside of a cylindrical chamber containing a rotating drum 38 cm (15 inches) in diameter. The substrates are mounted on a rotating drum and are sequentially passed through a position in front of the sputtering source by rotation of the drum at a speed of 1 to 8 rpm. The sputter source is suitably shielded so that the sample is not coated by either sputter stream at the same time. The rate of material deposition and the rate of substrate movement in front of the target determine the thickness of each individual layer comprising the final catalyst particles. Any vacuum pump capable of drawing a sufficient vacuum may be used. One such vacuum pump is the Varian AV8 cryopump (Varian Associates, Lexington, Mass.), which may be used in conjunction with an Alactel2012A rotary vane roughing pump (Alactel vacuum Products, Hingham, Mass.). The cryopump can be partially isolated from the sputtering chamber by a butterfly valve. During deposition, the pressure was maintained at 0.28 pa (2.1 mtorr) and the sputter gas flow rate was controlled by MKS flow controllers (MKS Instruments inc., Andover, MA). Any inert or reactive sputtering gas may be used. Argon or a mixture of argon and oxygen is preferably used. Oxygen stoichiometry can be controlled by varying the argon/oxygen flow ratio during Pt or Ru deposition. Any suitable target and power source may be used. In one embodiment, a three inch target is used. (Target materials, Columbeus, OH). The target was bonded to a copper substrate with indium from a 0.76 cm (0.3 inch) target material, which is standard practice in the field of sputter deposition. In one embodiment, an Advanced Energy MDX500 power supply (Advanced Energy industries, inc., Fort Collins, CO) is used in a constant power mode of the power supply.
The shape, morphology or crystal habit of the catalyst particles of the invention is new, the way in which different chemical elements are distributed in the particles (in the case of alloy catalysts) is new, the way in which the shape or size of the particles changes with increasing catalyst loading is new, and the way in which the particles are distributed on the support is also new. These characteristic differences are very important because it is generally known that catalyst activity is highly correlated with structure. Thus, the chemical composition of a catalyst is not the only, and often not the most important, feature in determining its effectiveness in heterogeneous catalysis. The catalytic reaction occurs on the surface of the catalyst, and therefore, the surface composition and surface structure of the catalyst, rather than its in vivo composition and structure, are very important.
The geometric surface area of the catalyst of the present invention can be estimated by counting the number of nano-sized acicular catalyst particles protruding per unit area of the PR149 catalyst support particle side in fig. 2, from the known length of the PR149 support particles and the known number of PR149 support particles per unit substrate planar area. PR149 Carrier particles at about 3-4X 109Number density growth per square centimeter of substrate. These needle-like whiskers were approximately regular hexahedron in shape, approximately 1.5 microns long, 50 nm wide, and 25 nm thick. As can be estimated from FIG. 2, each of the acicular catalyst particlesOccupying about 100 square nanometers of surface area of each PR149 support whisker since about 15 such particles per 150 nanometers of length of the whisker are seen. In the sample of fig. 2, the support particles are covered by catalyst particles over a length of about 1 micron in this manner. For smaller catalyst acicular particles, each PR149 whisker provides about 1.5 x 105Square nanometer ofGeometric surface area. This means that there are approximately 1500 such catalyst particles coating the sides of each support particle. If each such catalyst particle is considered to be approximately cylindrical, as shown in FIG. 2, with a diameter D and a length L, the geometric surface area is π DL, and the average D of these particles in FIG. 2 is 8.3 nanometers and the average L is 33 nanometers. The surface area of each such particle is about 860 square nanometers. The total geometric surface area of the catalyst per square centimeter of substrate is then 3X 109Whiskers/square centimeter × 1500 catalyst particles/whiskers × 860 square nanometers/catalyst particles, i.e., 3.9 × 1015Square nanometers per square centimeter, i.e., 39 square centimeters per square centimeter. For comparison, the geometric surface area of conventional spherical catalyst particles with a known particle size distribution on carbon particles per square centimeter of carbon-coated electrode substrate was calculated (Mizuhata et al, electrochemical society Proceedings 1995, Vol.95-23, p.24). This area is directly proportional to the catalyst loading per unit area of the substrate, and they give an increase in surface area of 1.948 square centimeters per square centimeter for a loading of 0.4 milligrams per square centimeter (see table i of the previous reference). Thus, the inventive nanostructured catalyst shown in fig. 2 provides an increase in specific geometric surface area of about 20 times that of conventional catalyst particles for about the same total catalyst loading.
The method and apparatus of the present invention allow selective modification of the stoichiometry, degree of alloying, degree of crystallization, grain morphology, and surface composition of the catalyst coating as a whole. These changes can be achieved by varying the relative deposition rate, power, throw distance of the monolayer, or time of passage before any source. In addition, other components may be added to the sputtering gas to alter the composition and structure of the catalyst. Any known additive to the sputtering gas, whether reactive or non-reactive with the deposited material, and whether incorporated into the catalyst as a constituent or as a dopant, may be used. The additives may include inert gases, halogens, group VII elements, preferably argon and oxygen. If the different vacuum deposition stations are sufficiently separated, a layered mixture may be produced incorporating the additive only in selected layers or incorporating different additives in different layers.
In one embodiment using additives, the method and apparatus of the present invention can be modified to selectively alter the crystallization characteristics of the catalyst coating. In a preferred embodiment, a method of producing an all-platinum nano-scale catalyst can be changed from obtaining a highly crystalline product to obtaining a completely amorphous product by adding oxygen to the sputtering gas composition. The amorphous catalyst particles see the same growth morphology of the columnar or needle-shaped catalyst particles as the crystalline catalyst particles. FIG. 3 shows amorphous PtO coated onto PR149 support particlesxSuch nodular growth of (a). The platinum catalyst should be used with an oxygen to argon ratio of at least 1: 1, more preferably 10: 1. Alternatively, a layered mixture of crystalline and amorphous catalysts may be produced by: oxygen is added to the sputtering gas composition of some, but not all, of the vacuum deposition stations if the different vacuum deposition stations are sufficiently separated.
The method and apparatus of the present invention can produce catalyst particles having a preferred final surface layer composition independent of the bulk composition. This can be achieved by varying the deposition conditions at the time of deposition of the final surface layer. The new conditions should be applied at least during the last deposition step, preferably at a thickness corresponding to the last 1-50, more preferably 1-20 monolayers deposited. The new conditions may include: shutting down any one of the operating deposition stations to stop its catalyst deposition, opening a new deposition station to deposit new catalyst, turning up or down the power of any one of the deposition stations, adding or subtracting certain additives to the sputtering gas of any one of the deposition stations, or any other means that can provide the desired change in the final surface layer composition or structure.
A preferred embodiment shows improved CO tolerance when used in the anode of a hydrogen fuel cell. This preferred embodiment of CO tolerance can be achieved with the above method, wherein alternating layers of Pt and Ru are deposited using a mixture of Ar/O as the sputtering gas. Preferably, an Ar/O ratio of 1: 1 to 1: 10, most preferably 1: 2, is employed. The catalyst is primarily alternating layers of Pt and Ru doped with oxygen, but may also contain other elements that do not adversely affect the performance of the catalyst. The Pt to Ru atomic ratio in the bulk catalyst composition is preferably between about 2: 1 and 1: 5. More preferably, between about 1: 1 and about 1: 2. Reducing or stopping the deposition of Ru, or increasing the deposition of Pt, at the end of the deposition step (more preferably at the end of the 1-10 passes, most preferably at the end of the 1-3 passes) can cause the composition of the growth surface to differ from the bulk composition. Most preferably, the Ru deposition is stopped at the final stage of the deposition step. Thus, the composition of the growth surface is richer in Pt than the bulk composition; i.e. less than 1 part Ru per part Pt. More preferably, the weight fraction of Ru in the growth surface is less than about 2/3, and even more preferably less than 40%, per weight fraction of Pt.
The invention can be used in electrochemical devices employing membrane electrodes optimized for this purpose, such as fuel cells, batteries, electrolyzers, electrochemical reactors such as chlor-alkali separation membranes, or gas, vapor or liquid sensors. The invention can be used in electrochemical devices with advantageous CO tolerance.
Objects and advantages of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention.
Examples
In some of the following examples, a catalyst support having a microstructure was prepared according to the method described in U.S. Pat. No. 5,338,430, which is incorporated herein by reference. Nanostructured perylene red (PR149, American Hoechst corp., Somerset, NJ) films on polyimide substrates were prepared using thermal evaporation deposition of an organic pigment c.i. pigment Res 149 (i.e., N' -di (3, 5-xylyl) perylene-3, 4, 9, 10 bis (dicarboximide)) and vacuum annealing according to the techniques described in U.S. patents 4, 812, 352 and 5, 039, 561. After deposition and annealing, a highly oriented crystal structure is formed having a large aspect ratio, a controllable length of about 0.5 to 2 microns, a width of about 0.03 to 0.05 microns, a density of about 30 whiskers per square micron area, oriented substantially perpendicular to the polyimide substrate. The microstructured carrier is non-conductive and is easily separated from the polyimide substrate when pressed into the ICM.
In some of the following examples, Pt and Ru catalyst coatings were applied to PR149 support particles by sputter deposition using a vacuum system as shown in fig. 4A. The apparatus consisted of a three source magnetron sputtering system arranged around a cylindrical sputtering chamber having an inner mounting diameter of 38 cm (15 inches) of a rotating drum. The substrate is mounted on a rotating drum and rotated sequentially through positions in front of each sputtering source at a speed of 1 to 8 rpm. The sputter source is suitably shielded so that the sample is not coated by either sputter jet at the same time. The vacuum pump used was a Varian AV8 cryopump (Varian Associates, Lexington, MA) equipped with an Alactel2012A rotary vane rough vacuum pump (Alactel vacuum Products, hindham, MA). The cryopump is partially isolated from the sputtering chamber by a butterfly valve. During deposition, the pressure was maintained at 0.28 Pa (2.1 mTorr), and the sputter gas flow rate was controlled by a MKS flow controller (MKSinstruments Inc., Andover MA). The sputtering gas used is argon or an argon/oxygen mixture. By varying the argon/oxygen flow ratio in Pt or Ru deposition, the stoichiometry of oxygen in the sputtered deposited layer can be controlled. A three inch Target (Target materials, Columbeus, OH) consisting of a 0.76 cm (0.3 inch) Target material bonded with indium on a copper substrate was used. An Advanced Energy MDX500 power supply (Advanced Energy Industries, inc., Fort Collins, CO) in a constant power mode was used for each deposition.
After deposition, the catalyst loading was determined by a simple gravimetric method. The nanostructured film layer samples supported on polyimide were weighed with a digital balance accurate to 1 microgram. The nanostructured layer is then wiped off the polyimide substrate with paper or linen and the substrate is reweighed. Since one preferred property of the nanostructured catalyst support is that it is easily transferred completely to the ion exchange membrane, it is also easily removed by simply wiping with a cloth. The weight per unit area of the catalyst support particles without Pt was also determined in this way. Nanostructures for use in the anode (hydrogen reaction electrode of a fuel cell) were prepared as described in the examples below. Nanostructures for cathodes (oxygen reaction electrodes of fuel cells) are made by: the nanostructures were pre-coated with about 0.02 mg/cm of carbon using argon as the sputtering gas to deposit the Pt. The catalyst loading varied between 0.09 and 0.425 mg/cm.
The ion-conducting membrane is a perfluorinated sulfonic acid material, specifically NafionTM117 films (DuPont Chemicals, Wilmington, DE, available from ElectroChem, inc., Woburn, MA, and Aldrich Chemical co., inc., Milwaukee, WI).
Before use, the Nafion membrane was pretreated by sequentially immersing in the following solutions: a) boiling water for 1 hour, b) boiling 3% H2O21 hour in boiling ultrapure water, c) 1 hour in boiling ultrapure water, d) 1 hour in boiling 0.5M sulfuric acid, e) 1 hour in boiling ultrapure deionized water. Nafion was then stored in ultrapure deionized water until use. Nafion was placed between several layers of clean linen and allowed to stand at 30 c for 10-20 minutes to dry before it participated in the formation of MEA.
Each MEA was made using a static pressure process that involved pressure transfer of the catalyst coated nanostructured elements to a Nafion 117 membrane by pressure transfer under vacuum at 130 ℃ and 160 megapascals (11.6 tons per square inch).To prepare an MEA with an active area of 5cm square by hydrostatic pressure, two 5cm pieces of polyimide substrate were placed2The square pieces of nanostructured elements (one for the anode and one for the cathode) were placed on each side of the center of a 7.6 cm x 7.6 cm Nafion 117 membrane. On both sides of such a sandwich of catalyst coated substrate/Nafion/catalyst coated substrate polyimide sheets with a thickness of 50 microns, 7.6 cm x 7.6 cm were placed. The assembly was then placed between two steel backing plates and pressed at a low vacuum at 130 ℃ with a Carver lab press (Carver inc., Wabash, IN) at a pressure of 160 megapascals (11.6 tons per square inch). Applying a low vacuum (Less than about 2 torr) to remove air from the stack prior to applying the maximum pressure. The initial 5 square centimeters of polyimide substrate was then peeled off to attach the catalyst to the Nafion membrane surface.
0.4 cm (0.015 ") thick ELAT was used on both catalyst electrodes of the MEATMElectrode backing layer (E-tek, Inc., Natick, MA) was covered and then placed on Teflon (R) 250 microns thickTMA 5 square centimeter square hole of a coated fiberglass mat (The furonco., CHR Division, New Haven, CT) was cut to fit The catalyst area. The flat electrode backing layer is referred to as "carbon only", i.e. it contains no catalyst. The constructed MEA was then mounted in a Cell (Fuel Cell Technologies, inc., Albuquerque, NM) of a test rig. The test station includes a variable electronic load and separate anode and cathode gas treatment systems for controlling gas flow, pressure and humidity. The electronic load and the gas flow are controlled by a computer.
The fuel cell polarization curves were obtained under the following test parameters: the electrode area is 5 square centimeters; cell temperature was 75 ℃ and anode gas pressure (gauge) was 62.0 kilopascal (9 psig); the anode gas flow rate is 75-150 standard cc/min; the anode humidifying temperature is 105 ℃: cathode pressure (gauge) 414 kilopascals (60 psig); the cathode flow rate was 600 standard cc/min; the cathode humidification temperature was 65 ℃. Humidification of the gas stream is performed by passing the gas through a spray bottle maintained at a specified temperature. Each fuel cell was brought to operating conditions of 75 ℃ under a flow of hydrogen and oxygen. After 24 hours of operation, the test procedure was started and the following parameters were determined: anode pressure, anode flow, cathode pressure, cathode flow, cell temperature, and CO concentration.
The surface chemical metrology data of the catalyst deposit was determined by X-ray photoelectron spectroscopy (XPS) using a device equipped with AlKαMonochromator model Hewlett-Packard model 5950A ESCA system (Hewlett-Packard Co., Palo Alto, CA). XPS is a non-destructive method for determining the elemental composition of the surface of a material, based on determining the kinetic energy of excitation of photoemitted electrons from the atomic core level by soft X-rays. LaunchingCan be detected at different angles relative to the sample surface; those electrons detected at approximately 0 deg. indicate the elemental composition of the closest surface (i.e., approximately 5_ deep) position. The samples used were from deposits on a reference plate (witness slide) (see example 1 below).
The samples were examined by X-ray diffraction using a Philips vertical diffractometer (reflection geometry), copper KαProportional detectors of radiation and scattered radiation (Philips Electronic Instruments co., Mahwah, NJ). The diffractometer was equipped with a variable entrance slit, a fixed exit slit, and a graphite diffracted beam monochromator. By double-sided coatingThe tape of (2) fixed the sample on a glass holder. Step scans were performed in a 35 to 90 degree (2 theta) scatter angle range with a step size of 0.06 degrees and a dwell time of 16 seconds. The generator was set at 40kV and 35 mA. By subtracting a representative sample, NafionTMThe data set obtained was scanned in a similar manner to remove background scatter due to the polymer matrix and the glass support. The results were analyzed with Philips PC-APD software. After correcting for the spread of the instrument, the Secherrer equation was used to determine the apparent grain size from the observed peak width, which was taken as the full width at the peak (FWHM) at half the peak height.
The overall composition was determined byenergy dispersive fluorescence analysis (EDAX). The assay was performed using an Amway scanning electron microscope with a silicon-based X-ray detector array using Tracor Northern counting electronics and software. The samples used were from deposits on reference plates (see example 1 below) or from whiskers removed from the substrate with dental cement. The electron beam of a scanning electron microscope produces X-rays when it strikes a sample. The energy of an X-ray depends on the atomic electronic structure of the material it strikes. X-ray energy between 0 and 10keV is taken at a fixed beam flow over an interval of 100 seconds. Fitting the data, after subtracting the background value, the ratio of the Pt-La peak (2.051 eV) to the Ru-La peak (2.558 eV) provides the atomic ratio of the bulk material.
EXAMPLE 1 preparation of the catalyst
The atomic ratio of Ru to Pt for the overall composition was 50: 50, and the surface composition of Pt, Ru and O was 63: 0: 34 (samples 1-9)) The anode catalyst composition of (a) was prepared as follows: a 50 micron polyimide film with PR149 support elements for the nanostructured catalyst (prepared as described above) deposited on a 38 cm diameter drum mounted in a vacuum system as described above and in fig. 4A. Another piece of polyimide was fixed in the system for use as a reference piece for XPS and EDAX assays. The system was coarsely depressurized to 0.27 Pa using a rotary vane pump, at which point the pump was closed and the gate valve was opened to the cryopump. The system was evacuated to about 1.3X 10-3A butterfly valve is then placed between the gate valve and the cryopump to achieve a maximum chamber pressure, typically in the range of 0.027 pa. The purpose of the butterfly valve is to separate the cryopump from the higher pressure part of the chamber. The mass flow controller was set to sputter argon at 8sccm and sputter oxygen at 16 sccm. The flow rates of each gas were adjusted to achieve a steady state chamber pressure of 0.28 Pa, with the flow ratio being maintained at 2: 1 oxygen to argon. The power supply for each sputtering source was then set to constant power with 175 watts for the Pt source and 285 watts for the Ru source. The drum was rotated at a speed of 3 rpm. Both power sources participate simultaneously. During deposition, a slight adjustment of the gas flow was required to maintain a pressure of 0.28 Pa. The deposition was continued for 10 minutes or 30 passes under each source, after which the Ru source was turned off. The Pt source was allowed to continue operating for 1 minute, which corresponds to three further passes without Ru sputter flow. Subsequent measurements of the film showed a loading of 0.09 mg/cm. The overall composition of Pt to Ru was 50: 50 as determined by energy dispersive X-ray analysis. The apparent crystal grain sizes were measured to be (111) 5 nm in lattice plane, (220) 3.3 nm in lattice plane, and (311) 3.8 nm in lattice plane, and the degree of alloying was very high by X-ray diffraction analysis. The results of XPS analysis of the reference plate showed that the emission wasThe Ru: Pt ratio was 0.037 at an electron angle of 38 ℃ to the sample surface and no Ru at 18 ℃ indicating that only PtO was present on the surfacex。
Many catalyst materials were prepared in a similar manner, with the ratio of Ru to Pt varying with the oxygen to argon ratio. The preparation results are shown in table 1.
TABLE 1
Sample (I) | Bulk Ru/Pt Atomic ratio | Ru/Pt at 38 ° Ratio of | Ru/Pt at 18 ° Ratio of | Surface oxygen at 38 ° Percent by weight |
1-1 | 54∶46 | 0.260 | 0.271 | 38 |
1-2 | 54∶46 | 1.040 | 1.330 | 47 |
1-3 | 56∶44 | 0.926 | 0.962 | 48 |
1-4 | 56∶44 | 1.292 | 1.381 | 45 |
1-5 | 55∶45 | 0.131 | 0.100 | 30 |
1-6 | 56∶44 | 0.141 | 0.134 | 64 |
1-7 | 50∶50 | 0.319 | 0.286 | 32 |
1-8 | 50∶50 | 0.114 | 0.147 | 37 |
1-9 | 50∶50 | 0.037 | 0.000 | 34 |
As can be seen from the data in Table I, samples 1-9 correspond to the detailed description of the procedure described above. The data in Table I show that for a given overall composition, the surface composition of a planar reference plate (i.e., a sample without microstructure) can be made Pt-rich or Ru-rich by selecting the source that is last directed to the target and the number of times the target is exposed to the last source. For example, for samples 1-7, 1-8, and 1-9, the target was passed under the Pt source 1, 2, and 3 more times, respectively. The method can also control the oxygen content on the surface of the catalyst. For example, samples 1-6 have an oxygen to argon ratio of 10: 1, while samples 1-7 have this ratio of 4: 1, which reflects the surface percentage of oxygen content in each sample. This indicates that the composition of the growth surface is controlled.
Example 2 PtRu vs PtRuOxHigh CO tolerance of
MEAs with different anode catalyst compositions were prepared and tested as described above. The composition is given in table iii. FIG. 5 compares Pt/Ru and PR/RuOx8 samples with a composition in a range were contacted with H containing 31-37.5 ppm CO2Polarization curves when and the response of two of the samples to pure hydrogen. The data in FIG. 5 show that PtRu and PtRuO are usedxThe compounds act as a difference in CO tolerance between fuel cell catalysts. The deposition method of the invention can convert the surface oxygen numberThe value X is controlled between 1 and 2. In all cases with oxygen as the sputtering gas, it can be seen that the cell performance in the presence of CO is improved over pure argon sputtering. Surprisingly, the most resistant anode composition isVery rich in Pt, while those compositions closer to 50/50 Pt/Ru show the worst performance in between. This is in contrast to the results disclosed for conventional carbon particle supported Pt/Ru catalysts.
TABLE III
Sample (I) | Pt/Ru/O |
1-A | 35/65/0 |
1-B | 50/50/0 |
1-C | 25/26/49 |
1-D | 53/18/29 |
1-E | 57/5.7/37 |
1-F | 53/18/29 |
1-G | 35/65/0 |
1-H | 42/22/36 |
1-I | 34/30/36 |
1-J | 42/22/36 |
Example 3 Pt-rich growth surface
Catalyst structures according to the invention were prepared with a 50: 50 overall Ru/Pt ratio and different Pt contents on the outer growth surface (measured by XPS at an angle of 38 ℃ C.). A fuel cell was assembled using an MEA containing the catalyst structure, and the polarization curves were measured as described above using hydrogen containing 35, 100 and 322ppm CO in the anode portion. The results are shown in Table IV. In each case, the loading was 0.09 mg/cm.
TABLE IV
Sample (I) | Delta V 35ppm CO | Delta V 100ppm CO | Delta V 322ppm CO |
1-7 | 180mV | NA | NA |
1-8 | 0 | 0 | 320mV |
1-9 | 0 | 0 | 0 |
In Table IV, "Delta V" represents the cell voltage drop for each MEA containing a sample of catalyst prepared as described in example 1 when exposed to CO at the indicated concentration at a current density of 0.7V compared to pure hydrogen. As shown in Table I, the outermost layer of samples 1-9 had at least three times as much Pt as samples 1-7 with aRu/Pt ratio of 0.319, and was substantially free of Ru. The data in Table IV show that the overall Pt to Ru ratio is 50: 50 while the anode catalyst of the present invention having a very high outermost Pt content is unaffected by exposure to 322ppm CO in hydrogen.
Example 4
This example, as well as the following comparative examples, demonstrate that the CO tolerance of nanostructured catalysts is improved over conventional carbon supported catalysts when applied to MEAs in the same manner without additional ionomer and tested under the same conditions.
The nanostructured anode catalyst was prepared as follows. A PR149 nanostructured film was prepared as described above on a polyimide substrate and sputter coated with alternating layers of Pt and Ru in an argon/oxygen mixture using a rotating drum as described above and shown in fig. 4A mounted in a vacuum system with a diameter of 38 cm, resulting in a nominal PR/Ru bulk composition of 35/65 weight percent. Only the Pt target was run during the last two revolutions of the drum, resulting in a Pt-rich surface composition with a standard Pt/Ru/O weight percent of 57: 6: 37 as measured by the XSP method for reference plate. The loading was measured to be about 0.09 mg/cm.
A cathode catalyst was prepared as another nanostructured PR149 whisker film sputter coated with 0.01 mg/cm carbon followed by 0.37 mg/cm Pt.
As described above, the two catalysts are then hot-pressed and transferred to opposite sides of the Nafion 117 membrane. These nanostructured membranes were used as anode and cathode catalysts to make 5cm square MEAs, where the nanostructured catalyst support particles were directly embedded in the Nafion membrane, and no ionomer was added to either the nanostructured membrane or the Nafion membrane.
The MEA was tested in a fuel cell test setup as described above, with the anode in contact with hydrogen containing 100ppm CO. The anode/cathode gauge pressure was 62/414 kPa (9/16 psig) hydrogen/oxygen, flow was 75/600 sccm, and spray bottle humidification temperature was 105 deg.C/65 deg.C, respectively. The cell temperature was 75 ℃. The cell was first run under pure hydrogen until it was stable and then switched to contact with hydrogen containing 100ppm CO and the cell current was measured at 0.7 volts at various times when the test stand was run in constant voltage mode. No polarization scan was performed during the test period of more than two hours. The current density as a function of time is shown in fig. 6, which shows a decrease in performance from about 0.52 amps/cm to about 0.45 amps/cm over the first 20 minutes, but a more gradual decrease to about 0.425 amps/cm over the next 2 hours. This performance is shown in figure 6 to be far superior to MEAs with much higher loadings of commercial carbon supported PtRu catalyst on the anode tested under the same conditions.
Example 5 (comparative example)
A catalyzed gas diffusion electrode was obtained from E-tek, Inc. and consisted of 20% by weight Pt: Ru (1: 1 atomic ratio) catalyst on Vulcan XC-72 carbon particles coated on ELATTMCarbon fiber cloth electrode backing. On receipt, catalyst and ELATTMNo ionomer was added to the membrane. The loading was 0.37 mg/cm. The catalyst side of the catalyst-containing membrane square piece was placed near the center of the Nafion 117 membrane as an anode to produce a 5cm square MEA. 5cm square Pt-coated nanostructured thin film sheet prepared in example 4 was placed onThe opposite side of the Nafion membrane was placed as the cathode. The sandwich was hot pressed using the same procedures and conditions used for transferring the catalyst in the previous examples. The MEA was tested for CO tolerance at 100ppm using the same conditions and test procedures used in example 4. FIG. 6 shows the current density of the comparative MEA at 0.7 volts as a function of timeAnd (5) changing the situation. The data in fig. 6 show that, despite its much higher loading (0.37 mg/cm), the current density of the carbon particle-supported PtRu catalyst of the comparative example suddenly dropped from 0.43 a/cm to 0.025 a/cm during the first 20 minutes of CO contact, and then continued to gradually drop to 0.02 a/cm over the subsequent 2 hours. This performance is far inferior to the nanostructured membrane anode catalysts of the present invention.
Example 6
This example demonstrates that the mixed Pt/Ru acicular nanoscopic catalyst particles are true alloys and that different alloy phases (PtRu and PtRu) can be obtained by the method of the invention2) Mixed alloy phases can be obtained in the same sample.
A film of PR149 microstructured support particles based on polyimide was mounted on a rotatable drum of a sputtering vacuum system as described above. PR149 whiskers were about 1.5 microns long. The drum was rotated at 41.25 seconds per revolution and the argon sputtering pressure for each sample was 0.29 Pa (2.2 mTorr). Varying sputter target power and time in some of the following samples, different alloy compositions were obtained. For each sample, a single electrode MEA was hot pressed as described above, approximately 1 square centimeter of catalyst coated whiskers were hot pressed into a Nafion 117 membrane, which was used for X-ray diffraction analysis. The scattering intensity of the flat Nafion 117 sample was subtracted from the resulting X-ray diffraction (XRD) line spectrum as a background correction. The catalyst diffraction peaks were fitted with software to obtain information on the presence and type of alloy forming the catalyst particles.
For sample 1, the Pt target was run at 175 Watts of power and the Ru target was run at 500 Watts for 25 minutes. Under these conditions, from the measured deposition rates for each target, the catalyst loading was calculated to be 0.13 mg/cm for Pt and 0.13 mg/cm for Ru. Energy dispersive X-ray (EDAX) fluorescence analysis in the SEM showed a Pt: Ru bulk composition of 35: 65 (atomic percent), which was calculated to be compatible with the loading, from the difference between the density of Pt (21.45 g/cc) and the density of Ru (12.2 g/cc). XRD showed that the catalyst particles consisted of two crystalline phases. One phase is the Pt Face Centered Cubic (FCC)) -type crystal structure containing about 70 atomic percent of Ru, indicating an alloy composition of PtRu2. The second phase was the pure Ru phase (with some evidence of possible Pt substitution). The grain size of the first phase was 130. ANG.according to the diffraction order of (111). The grain size of the second phase was 128A based on the Ru (111) peak.
For sample 2, the Pt target was run at 185 watts of power and the Ru target was run at 300 watts for 25 minutes. Under these conditions, the loading of Pt was calculated to be 0.14 mg/cm and the loading of Ru was calculated to be 0.08 mg/cm. EDAX fluorescence analysis in the SEM showed a Pt: Ru bulk composition of 50: 50 (atomic percent). XRD showed that the crystal grains consisted of a single crystalline phase, which was a Pt FCC type crystal structure containing about 54 atomic percent Ru, indicating that the alloy composition was PtRu. The grain size of the alloy was 114. ANG.according to the diffraction order of (111).
For samples 3-8, two similar sets of samples were made with different target powers and deposition times to obtain different loading amounts of the mixed alloy. Table V summarizes the preparation conditions and resulting alloy compositions for samples 3-8 along with samples 1 and 2.
TABLE V
Sample (I) | Pt power Tile | Ru work Rate of change Tile | Time of day Minute (min) | Total load capacity mg/cm2 | Pt∶Ru Atom% | Phase (C) | Alloy (I) (111) |
1 | 175 | 500 | 25 | 0.26 | 35∶65 | PtRu2+Ru | 130_ |
2 | 185 | 300 | 25 | 0.22 | 50∶50 | PtRu | 114_ |
3 | 175 | 450 | 35 | 0.34 | 35∶65 | PtRu2+Ru | 105_ |
4 | 175 | 450 | 17.5 | 0.165 | 35∶65 | PtRu2+Ru | 72_ |
5 | 175 | 450 | 6 | 0.046 | 35∶65 | PtRu2+Ru | 38_ |
6 | 175 | 285 | 35 | 0.23 | 50∶50 | PtRu | 65_ |
7 | 175 | 285 | 17 | 014 | 50∶50 | PtRu | 55_ |
8 | 175 | 285 | 6 | 0.044 | 50∶50 | PtRu | 36_ |
The data in Table V show that the same alloy composition was obtained at all loadings in each of the four samples having the same Pt: Ru ratio.
Various changes and modifications to the invention will become apparent to those skilled in the art without departing from the scope and theory of the invention, and it should be understood that this invention is not to be unduly limited to the illustrative examples set forth herein.
Claims (10)
1. Nanostructured elements comprising acicular, fibrous structures, support whiskers bearing acicular, nanoscopic catalyst particles.
2. The nanostructured elements according to claim 1, wherein the acicular nanoscopic catalyst particles comprise alternating layers of different catalyst materials.
3. The nanostructured elements according to claim 2, wherein the acicular nanoscopic catalyst particles comprise alternating layers of Pt-containing catalyst and Ru-containing catalyst.
4. The nanostructured elements according to claim 1, wherein the composition of the growth surface of the acicular nanoscopic catalyst particles is different from the bulk composition of the acicular nanoscopic catalyst particles.
5. The nanostructured elements according to claim 4, wherein the acicular nanoscopiccatalyst particles comprise Pt and Ru, wherein the composition of the growth surface of the acicular nanoscopic catalyst particles comprises a Pt/Ru ratio higher than the bulk composition of the acicular nanoscopic catalyst particles.
6. A method of making a nanostructured element according to claim 2 or 3, which comprises the step of repeatedly alternating vacuum deposition of at least two different catalyst materials onto acicular microstructured support whiskers.
7. A method of making a nanostructured element according to claim 4 or 5, which method comprises the steps of: repeatedly and alternately vacuum depositing at least two different catalyst materials onto acicular microstructured support whiskers, and then vacuum depositing at least one, but less than all, of said catalyst materials onto said acicular microstructured support whiskers.
8. A carbon monoxide tolerant nanostructured element comprising the nanostructured element according to claim 3 or claim 5, wherein the weight ratio of Pt to Ru on the catalyst growth surface is greater than 1: 1, and the weight ratio of Pt to Ru of the catalyst material as a whole is between 1: 2 and 1: 1.
9. A carbon monoxide tolerant catalyst comprising Pt and Ru, wherein the weight ratio of Pt to Ru on the catalyst bulk is less than 1: 1 and the weight ratio of Pt to Ru on the catalyst surface is greater than 1: 1.
10. An electrochemical cell comprising a nanostructured element according to any one of claims 1 to 8.
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Also Published As
Publication number | Publication date |
---|---|
US6040077A (en) | 2000-03-21 |
KR20050072150A (en) | 2005-07-08 |
EP1021246A1 (en) | 2000-07-26 |
US5879827A (en) | 1999-03-09 |
JP4837822B2 (en) | 2011-12-14 |
KR100570136B1 (en) | 2006-04-12 |
DE69824875T2 (en) | 2005-07-07 |
JP2001519594A (en) | 2001-10-23 |
CA2304157A1 (en) | 1999-04-22 |
EP1021246B1 (en) | 2004-06-30 |
KR20010031023A (en) | 2001-04-16 |
KR100567198B1 (en) | 2006-04-04 |
AU7469698A (en) | 1999-05-03 |
WO1999019066A1 (en) | 1999-04-22 |
DE69824875D1 (en) | 2004-08-05 |
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